Self-Organized SERS Substrates with Efficient Analyte Enrichment in the Hot Spots.

One of the requirements of an efficient surface-enhanced Raman spectroscopy (SERS) substrate is a developed surface morphology with a high density of "hot spots", nm-scale spacings between plasmonic nanoparticles. Of particular interest are plasmonic architectures that could enable self-localization (enrichment) of the analyte in the hot spots. We report a straightforward method of fabrication of efficient SERS substrates that comply with these requirements. The basis of the substrate is a large-area film of tightly packed SiO2 spheres formed by their quick self-assembling upon drop casting from the solution. Thermally evaporated thin Ag layer is converted by quick thermal annealing into nanoparticles (NPs) self-assembled in the trenches between the silica spheres, i.e., in the places where the analyte molecules get localized upon deposition from solution and drying. Therefore, the obtained substrate morphology enables an efficient enrichment of the analyte in the hot spots formed by the densely arranged plasmonic NPs. The high efficiency of the developed SERS substrates is demonstrated by the detection of Rhodamine 6G down to 10-13 mol/L with an enhancement factor of ∼108, as well as the detection of low concentrations of various nonresonant analytes, both small dye molecules and large biomolecules. The developed approach to SERS substrates is very straightforward for implementation and can be further extended to using gold or other plasmonic NPs.

SERS-substrates based on ZnO nanoflowers prepared by green synthesis.

ZnO nanoparticles (NPs) with a flower-like morphology, synthesized by an affordable colloidal route using an aqueous fungi extract of Ganoderma lucidum as a reducing agent and stabilizer, are investigated as SERS-substrate. Each "flower" has large effective surface that is preserved at packing particles into a dense film and thus exhibits an advantageous property for SERS and similar sensing applications. The mycoextract used in our low-cost and green synthesis as surface stabilizer allows subsequent deposition of metal NPs or layers. One type of SERS substrates studied here was ZnO NPs decorated in situ in the solution by Ag NPs, another type was prepared by thermally evaporating Ag layer on the ZnO NP film on a substrate. A huge difference in the enhancement of the same analyte in the solution and in the dried form is found and discussed. Detection down to 10-7 M of standard dye analytes such as rhodamine 6G and methylene blue was achieved without additional optimization of the SERS substrates. The observed SERS-activity demonstrate the potential of both the free-standing flower-like ZnO NPs and thereof made dense films also for other applications where large surface area accessible for the external agent is crucial, such as catalysis or sensing.

Core and Shell Contributions to the Phonon Spectra of CdTe/CdS Quantum Dots.

The parameters of the shell and interface in semiconductor core/shell nanocrystals (NCs) are determinant for their optical properties and charge transfer but are challenging to be studied. Raman spectroscopy was shown earlier to be a suitable informative probe of the core/shell structure. Here, we report the results of a spectroscopic study of CdTe NCs synthesized by a facile route in water, using thioglycolic acid (TGA) as a stabilizer. Both core-level X-ray photoelectron (XPS) and vibrational (Raman and infrared) spectra show that using thiol during the synthesis results in the formation of a CdS shell around the CdTe core NCs. Even though the spectral positions of the optical absorption and photoluminescence bands of such NCs are determined by the CdTe core, the far-infrared absorption and resonant Raman scattering spectra are dominated by the vibrations related with the shell. The physical mechanism of the observed effect is discussed and opposed to the results reported before for thiol-free CdTe Ns as well as CdSe/CdS and CdSe/ZnS core/shell NC systems, where the core phonons were clearly detected under similar experimental conditions.

Plasmonic colloidal Au nanoparticles in DMSO: a facile synthesis and characterisation.

We report a new pathway for the synthesis of plasmonic gold nanoparticles (Au NPs) in a bio-compatible medium. A modified room temperature approach based on the standard Turkevich synthesis, using sodium citrate as a reducing and stabilizing agent, results in a highly stable colloidal suspension of Au NPs in dimethyl sulfoxide (DMSO). The mean NP size of about 15 nm with a fairly low size distribution is revealed by scanning electron microscopy. The stability test through UV-vis absorption spectroscopy indicates no sign of aggregation for months. The Au NPs are also characterized by X-ray photoelectron, Raman scattering, and FTIR spectroscopies. The stabilisation mechanism of the Au NPs in DMSO is concluded to be similar to that of NPs synthesized in water. The Au NPs obtained in this work are applicable as SERS substrates, as proved by common analytes. In terms of bio-applications, they do not possess such side-effects as pronounced antibacterial activity, based on the tests performed on non-pathogenic Gram-positive or Gram-negative bacteria.

ZnO and Ag NP-decorated ZnO nanoflowers: green synthesis using Ganoderma lucidum aqueous extract and characterization.

Fungi produce and excrete various proteins, enzymes, polysaccharides, and secondary metabolites, which may be used as media for the "green" synthesis of metal and semiconductor nanoparticles (NPs). ZnO NPs with a flower-like morphology were synthesized by an affordable colloidal route, using an aqueous extract of Ganoderma lucidum as a reducing agent and stabilizer. Each individual "flower" has a large effective surface, which is preserved when the particles are close packed into a dense film, which is advantageous for numerous applications. The phonon Raman spectrum and X-ray diffraction (XRD) pattern prove the high crystallinity of the NPs, with the distinct pattern of a hexagonal (wurtzite) lattice, negligible residual stress, and a crystallite size of 12-14 nm determined from the XRD. The photoluminescence (PL) spectrum of the as-synthesized ZnO NPs contains a structured defect-related feature in the violet-blue range, while the green PL, common for nanostructures synthesized by "green" routes, is very weak. By applying dimethylsulfoxide as an additional passivating agent, the excitonic (UV) PL band was activated without enhancement of the defect-related features. Ag NP-decorated ZnO flowers were synthesized by subsequent silver reduction by pepper extract. The ZnO/Ag NPs exhibited efficient surface-enhanced Raman scattering (SERS) of a standard dye analyte, rhodamine 6G, ensuring the feasibility of other applications that require close contact of ZnO/Ag to other nanostructures or molecules to realize the energy of the charge transfer.

Spectroscopy and Theoretical Modeling of Phonon Vibration Modes and Band Gap Energy of Cu2ZnSn(S x Se1-x )4 Bulk Crystals and Thin Films.

Semiconductor Cu2ZnSn(S x Se1-x )4 (CZTSSe) solid solution is considered as a perspective absorber material for solar cells. However, during its synthesis or deposition, any modification in the resulting optical properties is hardly predicted. In this study, experimental and theoretical analyses of CZTSSe bulk crystals and thin films are presented based on Raman scattering and absorption spectroscopies together with compositional and morphological characterizations. CZTSSe bulk and thin films are studied upon a change in the x = S/(S + Se) aspect ratio. The morphological study is focused on surface visualization of the solid solutions, depending on x variation. It has been discovered for the first time that the surface of the bulk CZTSSe crystal with x = 0.35 has pyramid-like structures. The information obtained from the elemental analysis helps to consider the formation of a set of possible intrinsic lattice defects, including vacancies, self-interstitials, antisites, and defect complexes. Due to these results and the experimentally obtained values of the band gap within 1.0-1.37 eV, a deviation from the calculated band gap values is estimated in the range of 1.0-1.5 eV. It is suggested which defects can have an influence on such a band gap change. Also, on comparing the experimental Raman spectra of CZTSSe with the theoretical modeling results, an excellent agreement is obtained for the main Raman bands. The proposed theoretical approach allows to estimate the values of concentration of atoms (S or Se) for CZTSSe solid solution directly from the experimental Raman spectra. Thus, the visualization of morphology and the proposed theoretical approach at various x values will help for a deeper understanding of the CZTSSe structure to develop next-generation solar cells.

Colloidal Cu-Zn-Sn-Te Nanocrystals: Aqueous Synthesis and Raman Spectroscopy Study.

Cu-Zn-Sn-Te (CZTTe) is an inexpensive quaternary semiconductor that has not been investigated so far, unlike its intensively studied CZTS and CZTSe counterparts, although it may potentially have desirable properties for solar energy conversion, thermoelectric, and other applications. Here, we report on the synthesis of CZTTe nanocrystals (NCs) via an original low-cost, low-temperature colloidal synthesis in water, using a small-molecule stabilizer, thioglycolic acid. The absorption edge at about 0.8-0.9 eV agrees well with the value expected for Cu2ZnSnTe4, thus suggesting CZTTe to be an affordable alternative for IR photodetectors and solar cells. As the main method of structural characterization multi-wavelength resonant Raman spectroscopy was used complemented by TEM, XRD, XPS as well as UV-vis and IR absorption spectroscopy. The experimental study is supported by first principles density functional calculations of the electronic structure and phonon spectra. Even though the composition of NCs exhibits a noticeable deviation from the Cu2ZnSnTe4 stoichiometry, a common feature of multinary NCs synthesized in water, the Raman spectra reveal very small widths of the main phonon peak and also multi-phonon scattering processes up to the fourth order. These factors imply a very good crystallinity of the NCs, which is further confirmed by high-resolution TEM.

Structural and Dipole-Relaxation Processes in Epoxy-Multilayer Graphene Composites with Low Filler Content.

Multilayered graphene nanoplatelets (MLGs) were prepared from thermally expanded graphite flakes using an electrochemical technique. Morphological characterization of MLGs was performed using scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Raman spectroscopy (RS), and the Brunauer-Emmett-Teller (BET) method. DGEBA-epoxy-based nanocomposites filled with synthesized MLGs were studied using Static Mechanical Loading (SML), Thermal Desorption Mass Spectroscopy (TDMS), Broad-Band Dielectric Spectroscopy (BDS), and Positron Annihilation Lifetime Spectroscopy (PALS). The mass loading of the MLGs in the nanocomposites was varied between 0.0, 0.1, 0.2, 0.5, and 1% in the case of the SML study and 0.0, 1.0, 2, and 5% for the other measurements. Enhancements in the compression strength and the Young's modulus were obtained at extremely low loadings (C≤ 0.01%). An essential increase in thermal stability and a decrease in destruction activation energy were observed at C≤ 5%. Both the dielectric permittivity (ε1) and the dielectric loss factor (ε2) increased with increasing C over the entire frequency region tested (4 Hz-8 MHz). Increased ε2 is correlated with decreased free volume when increasing C. Physical mechanisms of MLG-epoxy interactions underlying the effects observed are discussed.

Photoinduced Enhancement of Photoluminescence of Colloidal II-VI Nanocrystals in Polymer Matrices.

The environment strongly affects both the fundamental physical properties of semiconductor nanocrystals (NCs) and their functionality. Embedding NCs in polymer matrices is an efficient way to create a desirable NC environment needed for tailoring the NC properties and protecting NCs from adverse environmental factors. Luminescent NCs in optically transparent polymers have been investigated due to their perspective applications in photonics and bio-imaging. Here, we report on the manifestations of photo-induced enhancement of photoluminescence (PL) of aqueous colloidal NCs embedded in water-soluble polymers. Based on the comparison of results obtained on bare and core/shell NCs, NCs of different compounds (CdSe, CdTe, ZnO) as well as different embedding polymers, we conclude on the most probable mechanism of the photoenhancement for these sorts of systems. Contrary to photoenhancement observed earlier as a result of surface photocorrosion, we do not observe any change in peak position and width of the excitonic PL. Therefore, we suggest that the saturation of trap states by accumulated photo-excited charges plays a key role in the observed enhancement of the radiative recombination. This suggestion is supported by the unique temperature dependence of the trap PL band as well as by power-dependent PL measurement.

Optical arrangement for surface plasmon-assisted directional enhanced Raman scattering spectroscopy.

We present an optical arrangement for spectroscopy of enhanced Raman scattering assisted by surface plasmon resonance in continuous planar metallic films. Optical excitation of propagating surface plasmons (PSP) is aided by the hemispherical total internal reflectance prism in the Kretschmann geometry. In this geometry, the radiation produced by Raman scattering is directionally emitted inside the prism with the angular distribution in the shape of a hollow cone (the Kretschmann cone). The proposed configuration enables entire collection of the Kretschmann cone with the use of an elliptical mirror modified for enlarging the accessible angular range for both the incident beam and the scattered light. The spectroscopic performance of this arrangement was evaluated using the Rhodamine 6G dye as a surface enhanced Raman scattering (SERS) reporter. An evident difference in magnitudes of the enhancement factor for specific spectral lines as compared to SERS excitation by localized surface plasmon resonance (LSPR-SERS) was revealed. The origin of this difference is discussed in terms of expected distinctions between the PSP-assisted directional enhanced Raman scattering and the LSPR-SERS. Besides the spectroscopic applications, the proposed arrangement is also perfectly suited for simultaneous functioning as the SPR sensor. Integration of SERS spectroscopy with the SPR analysis shows promise as a platform for evolving an innovative analytical technique with enhanced potentialities in surface research, particularly in biochemical applications.

Effect of non-stoichiometry of initial reagents on morphological and structural properties of perovskites CH3NH3PbI3.

The properties of films of organic-inorganic perovskites CH3NH3PbI2.98Cl0.02 depending on the ratio of starting reagents in solutions (PbI2:{CH3NH3I + CH3NH3Cl}) has been investigated. It was found that the formation of the perovskite structure with the ratio of the initial reagents PbI2: CH3NH3I = 1:1 occurs at 70-80 °C, and with the increase of the temperature of thermal treatment to 120 °C, the thermal destruction of the perovskite begins. When the ratio of the starting reagents PbI2: CH3NH3I = 1:2, the formation of the perovskite structure occurs through the intermediate compound (CH3NH3)2PbI4, and when the ratio is 1:3-(CH3NH3)3PbI5 and (CH3NH3)2PbI4. Independent on the ratio of the initial components (CH3NH3I:PbI2), the ratio between the content of lead and iodine in the films remains unchanged, that is why a significant difference in the film properties could be explained by the anisotropy of the particle shape, which is consistent with the data of electron microscopy and X-ray diffractometry.

Theoretical and Experimental Study of Phonon Spectra of Bulk and Nano-Sized MoS2 Layer Crystals.

Theoretical analysis of Raman scattering spectra (RS) for single-crystal MoS2 sample and atomically thin MoS2 sample consisting from one to few layers was performed in order to explain the change of MoS2 vibrations at transition from a monoatomic layer to a bulk crystal. Experiments have shown that changes of frequencies of the most intensive bands arising from the in-plane, [Formula: see text], and out-of-plane, A 1g , vibrations, as a function of number n of layers looks differently. Thus, the frequency of ω(A 1g ) is increasing with growth of n, whereas the frequency of [Formula: see text] is decreasing. Such a change of the [Formula: see text] frequency was explained as the effect of "strong increase of the dielectric tensor when going from single layer to the bulk" sample. In the present work, we show that the reason of different dependences of frequencies can be related to both the van der Waals (vdW) interlayer interaction and the anharmonic interaction of noted fundamental vibrations with the corresponding combination tones (CT) of layer that manifests itself due to Fermi resonance in the layer. Overjumping of these phonon pairs (s, s ') owing to interlayer interaction, [Formula: see text], to other layers at growth of number n, results in the change of frequencies for each interacting pair of A 1g or [Formula: see text] symmetry. The alteration of pair frequencies depends on the ratio of constants [Formula: see text] describing the interaction of studied states s and s '.

Raman spectroscopy of Cu-Sn-S ternary compound thin films prepared by the low-cost spray-pyrolysis technique.

Cu-Sn-S (CTS) thin films were deposited onto bare and molybdenum (Mo) coated glass substrates by means of the spray pyrolysis technique under different conditions. The CTS thin films obtained are shown, by means of Raman spectroscopy, to consist of two main phases: Cu2SnS3 and Cu3SnS4 as well as of the secondary phase of Cu2-xS. The electrical conductivity of the spray-deposited p-type CTS thin films under investigation is determined by two shallow acceptor levels: Ev+0.07 eV at T<334 K and Ev+0.1 eV at T>334 K. The material of the CTS thin films was established to be a direct-band semiconductor with the bandgap Eg=1.89 eV. The SEM and x-ray energy dispersive analysis show the surface and cross section of the CTS thin film deposited onto molybdenum-coated glass ceramics substrate with the actual atomic ratios of Cu:Sn:S being 2.9:1:2.64, which is in good agreement with the Raman spectra. Also, a small content of residual Cl atoms was found in the CTS thin films under investigation as the by-product of the pyrolytic reactions.

Direct Determination of 3D Distribution of Elemental Composition in Single Semiconductor Nanoislands by Scanning Auger Microscopy.

An application of scanning Auger microscopy with ion etching technique and effective compensation of thermal drift of the surface analyzed area is proposed for direct local study of composition distribution in the bulk of single nanoislands. For GexSi1 - x-nanoislands obtained by MBE of Ge on Si-substrate gigantic interdiffusion mixing takes place both in the open and capped nanostructures. Lateral distributions of the elemental composition as well as concentration-depth profiles were recorded. 3D distribution of the elemental composition in the d-cluster bulk was obtained using the interpolation approach by lateral composition distributions in its several cross sections and concentration-depth profile. It was shown that there is a germanium core in the nanoislands of both nanostructure types, which even penetrates the substrate. In studied nanostructures maximal Ge content in the nanoislands may reach about 40 at.%.

Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite.

Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp(2)-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width. The careful search of the nature of two other narrow electron paramagnetic resonance signals in shungite, which used to be prescribed to fullerene-like molecules, is fulfilled. Here, it is shown that the oxygen-deficient E'γ centers are responsible for these signals. A strong correlation is revealed between the concentration of Е'γ centers and the line width of conduction electron spin resonance signal, which occurs under annealing process of the samples at T = 570 K. The correlation reasons are a spin-spin coupling between two spin subsystems and time dependent of the Е'γ concentration during annealing process.